CN116282049A - 一种可控有序介孔二氧化硅微球的制备方法 - Google Patents
一种可控有序介孔二氧化硅微球的制备方法 Download PDFInfo
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Abstract
本发明公开一种可控有序二氧化硅微球的制备方法，采用壳聚糖季铵盐为结构导向剂、无机硅或者有机硅为硅源，在碱性条件下通过结构导向剂的正电荷和具有高负电荷密度的硅物种通过强静电相互作用组装在一起，之后通过焙烧去除掉模板剂，制备了具有有序均匀介孔结构、颗粒尺寸可控、形貌规整、比表面积大的二氧化硅微球，通过改变硅源调节硅球颗粒的大小。制备过程、工艺流程简单。铵盐壳聚糖的使用彻底解决了壳聚糖需要在酸性条件才水溶的问题，省略了酸化的步骤，简化了硅球的制备过程；同时其丰富的亲水氨基可以发挥结构导向剂的作用，从而制备介孔材料。采用无机硅源降低了合成成本，省略了添加醇类助溶的步骤，有利于该微球的工业应用推广。
Description
技术领域
本发明属于二氧化硅超微粒子制备技术领域，具体涉及一种可控有序介孔二氧化硅微球的制备方法，特别是一种尺寸可控的有序介孔氧化硅微球的制备方法。
背景技术
氧化硅微球是高新技术产业的重要新兴材料，随着近年来高新技术产业的蓬勃发展，高档次、高纯度、生物级氧化硅产品的市场需求逐年增加。介孔氧化硅微球由于密度低、硬度高、耐高温等优点，在药物缓释、太阳能电池、催化载体、耐高温材料等众多领域有着广泛的应用范围，是一种高附加值的材料。
目前合成二氧化硅球的方法有很多，例如：气相法、反相微乳法、气相沉积法、沉淀法、溶胶-凝胶法等。模板法是合成介孔二氧化硅不可忽视的方法，通常是采用表面活性剂作为制备微球的模板，结合水醇等混合溶剂，在模板的前提下制备出不同大小粒径的二氧化硅微球，而后经过洗涤、干燥、煅烧处理后得到介孔二氧化硅微球，介孔二氧化硅的硅源为有机硅。
天然生物材料壳聚糖经处理可以作为模板制备中空的氧化硅微球，此时的壳聚糖起到的是造孔剂的作用，也就是制备多级孔材料领域中硬模板的作用，制备完成通过焙烧去除壳聚糖从而得到中空结构。而且由于其水溶性的问题，需要经过乙酰化及酸化并交联处理才能作为模板剂使用，工艺复杂。近年来由于壳聚糖为天然多糖甲壳素脱除部分乙酰基的产物，具有生物降解性、无毒性、抑菌等等功能，被广泛应用于食品、农业、环保、药物缓释材料等众多领域和其他日用化学工业。因此其衍生物的研究也是一大热点。其中壳聚糖季铵盐是一种经海洋生物壳聚糖化学改性而制得的壳聚糖高级衍生物，属于天然生物制剂产品，近年来才被制备出来。壳聚糖季铵盐化后不但增强了壳聚糖的正电性，同时具备了良好的阳离子吸附性、水溶性等众多优点，此外还可以生物降解，但应用范围亟需开发。
发明内容
鉴于上述背景中的不足之处，本发提供了一种可控有序介孔二氧化硅微球的制备方法。本发明中以壳聚糖的季铵盐为结构导向剂，无机硅或有机硅为硅源，在碱性条件下通过结构导向剂的正电荷和具有高负电荷密度的硅物种通过强静电相互作用组装在一起。之后通过焙烧去除掉模板剂，得到具有均匀介孔结构的氧化硅微球。制备过程简单，操作方便，球形度好，粒径均匀，有机硅和无机硅的使用可以分别得到颗粒度范围不同的硅球，物料廉价易得。
本发明技术方案如下：
一种可控有序介孔二氧化硅微球的制备方法，包括如下步骤：
(1)将结构导向剂和去离子水混合均匀，得到溶液A；所述结构导向剂为壳聚糖的季铵盐；
(2)将有机硅源的醇溶液或无机硅源加入到溶液A中，搅拌均匀得到溶液B；
(3)在搅拌的状态下将矿化剂加入到溶液B中，得到乳液C，无机硅源体系中乳液C的物质摩尔比组成为SiO2：结构导向剂：矿化剂：H2O＝1：(0.0005-0.003)：(0.6-0.9)：(15-20)；有机硅源体系中乳液C的物质摩尔比组成为SiO2：结构导向剂：矿化剂：醇：H2O＝1：(0.0005-0.003)：(0.6-0.9)：(1.8-3.5)：(15-20)。
(4)将乳液C经过分离、洗涤、烘干、焙烧即得到可控有序介孔二氧化硅微球。
作为优选方案，步骤(1)中所述壳聚糖的季铵盐为羟丙基三甲基氟化铵壳聚糖、羟丙基三甲基氯化铵壳聚糖和羟丙基三甲基溴化铵壳聚糖中的一种或者多种的混合物，进一步地，分子量为20万，更进一步地，壳聚糖的季铵盐为羟丙基三甲基氟化铵壳聚糖。
作为优选方案，步骤(2)中所述无机硅源为碱性硅溶胶，其SiO2干基含量为20-50％；所述有机硅源为正硅酸四乙酯、正硅酸四甲酯、正硅酸四丙酯和正硅酸四丁酯中的一种或者多种的混合物。
作为优选方案，步骤(3)中所述矿化剂为氨水、十二胺、尿素、二乙醇胺、三乙胺和二乙胺中的一种或多种的混合物。
作为优选方案，步骤(1)中结构导向剂和去离子水的混合温度为40-80℃，进一步地，混合温度为50-70℃。
作为优选方案，步骤(4)中所述烘干温度为80-120℃，焙烧温度为500-650℃。
本发明的有益效果是：通过壳聚糖季铵盐为结构导向剂制备出了孔道尺寸为3nm、硅源不同可以得到球体直径分别为500-600nm和5μm的二氧化硅微球。壳聚糖季铵盐作为一种阳离子表面活性剂，保留了壳聚糖中存在大量羟基的结构，季铵化后的壳聚糖从根本解决了水溶性的问题，而且季铵化后具有很好的正电性和高的阳离子强度，可用作介孔结构的导向剂。在制备过程中壳聚糖季铵盐的亲水氨基在水溶液中形成胶束，硅物种在矿化剂的作用下水解成硅胶颗粒，在结构导向剂强的正电诱导下(氢键作用)，在胶束表面聚集成晶核，然后晶核进一步自组装缩合形成二氧化硅，之后通过焙烧去除结构导向剂得到介孔二氧化硅微球。有机硅是单聚体的硅物种，无机硅源为聚合态的硅物种，分别为硅源时所得到的硅球颗粒后者较前者的大。该制备工艺简单，条件温和，原材料廉价易得，制得的微球颗粒均匀、形貌规整、孔道有序，比表面积大。通过控制自组装和二氧化硅的缩合速率，调整二氧化硅微球的尺寸。季铵盐壳聚糖的使用彻底解决了壳聚糖需要在酸性条件才水溶的问题，省略了酸化的步骤，简化了硅球的制备过程；同时其发丰富的亲水氨基可以发挥结构导向剂的作用，从而制备介孔材料。采用无机硅源为硅源降低了合成成本，省略了添加醇类助溶的步骤，有利于该微球的工业应用推广。
本发明得到的有序介孔二氧化硅具有孔体积大和比表面积高的特点，可以作为特种药物(例如抗癌药物)和生物活性分子(例如蛋白质和核苷酸)的宿主材料。此外均匀的介孔结构和大的比表面积以及表面羟基多易于功能化使其成为吸附和保持药物有效或者生物活性的载体，另外在化工领域中在特定的反应中作为催化剂的载体亦有较好的应用前景。
附图说明
图1为1#样品的孔径分布图。
图2为1#样品的物理吸附谱图。
图3为1#样品的扫描电镜照片。
图4为2#样品的孔径分布图。
图5为2#样品的物理吸附谱图。
图6为2#样品的扫描电镜照片。
具体实施方式
以下实施例作为本发明的进一步说明，但本发明的内容不限于实施例中的内容。
实施例1
在50℃下，将25g分子量为20万的羟丙基三甲基氯化铵壳聚糖溶于36g水中，得到透明均匀的溶液。将24g正硅酸四乙酯溶于11.5g乙醇中后加入到上述透明溶液中，加入0.08mol的矿化剂搅拌40min，得到二氧化硅微球的悬浮液，经分离、洗涤、100℃烘干后在500℃下焙烧6h，得到二氧化硅微球1#，孔径分布图如图1所示其孔径为3nm。物理吸附谱图如图2所示，其为介孔结构，孔容为0.987m3/g，比表面积为1380m2/g，扫描电镜照片如图3所示，其颗粒直径为500-600nm。
实施例2
在50℃下，将25g分子量为20万的羟丙基三甲基氯化铵壳聚糖溶于39.55g水中，得到透明均匀的溶液。将14.9g碱性硅溶胶(JN-30,二氧化硅硅含量为30％)加入到上述透明溶液中，加入0.08mol的矿化剂搅拌40min，得到二氧化硅微球的悬浮液，经分离、洗涤、100℃烘干后在500℃下焙烧6h，得到二氧化硅微球2#，孔径分布图如图4所示，其孔径为3nm。物理吸附谱图如图5所示，其为介孔结构，孔容为0.814m3/g，比表面积为1395m2/g，扫描电镜照片如图6所示，其颗粒直径为5μm。
实施例3
重复实施例1的实验过程，只是将羟丙基三甲基氯化铵壳聚糖分别替换为羟丙基三甲基氟化铵壳聚糖和羟丙基三甲基溴化铵壳聚糖，保持物质的量不变。得到二氧化硅微球3#和4#，其孔径为3nm颗粒直径为500-600nm。
实施例4
重复实施例2的实验过程，只是将羟丙基三甲基氯化铵壳聚糖分别替换为羟丙基三甲基氟化铵壳聚糖和羟丙基三甲基溴化铵壳聚糖，保持物质的量不变。得到二氧化硅微球5#和6#，其孔径为3nm，颗粒直径为5μm。
实施例5
重复实施例1的实验过程，只是将正硅酸四乙酯分别替换为正硅酸四甲酯、正硅酸四丙酯和正硅酸四丁酯，保持物质的量不变。得到的二氧化硅微球颗粒孔径尺寸为3nm，颗粒直径为500-600nm。
实施例6
重复实施例1的实验过程，只是将矿化剂分别替换为氨水、十二胺、尿素、二乙醇胺、三乙胺和二乙胺，保持物质得量不变。得到的氧化硅微球其颗粒孔尺寸为3nm，颗粒直径为500-600nm。
实施例7
重复实施例2的实验过程，只是将矿化剂分别替换为氨水、十二胺、尿素、二乙醇胺、三乙胺和二乙胺，保持物质得量不变。得到的氧化硅微球其颗粒孔径尺寸为3nm，颗粒直径为5μm。
Claims (6)
1.一种可控有序介孔二氧化硅微球的制备方法，其特征在于：包括如下步骤：
S1将结构导向剂和去离子水混合均匀，得到溶液A；所述结构导向剂为壳聚糖的季铵盐；
S2将有机硅源的醇溶液或无机硅源加入到溶液A中，搅拌均匀得到溶液B；
S3在搅拌的状态下将矿化剂加入到溶液B中，得到乳液C，无机硅源体系中乳液C的物质摩尔比组成为SiO2：结构导向剂：矿化剂：H2O＝1：(0.0005-0.003)：(0.6-0.9)：(15-20)；有机硅源体系中乳液C的物质摩尔比组成为SiO2：结构导向剂：矿化剂：醇：H2O＝1：(0.0005-0.003)：(0.6-0.9)：(1.8-3.5)：(15-20)。
S4将乳液C经过分离、洗涤、烘干、焙烧得到可控有序介孔二氧化硅微球。
2.如权利要求1所述的一种可控有序介孔二氧化硅微球的制备方法，其特征在于：S1中所述壳聚糖的季铵盐为羟丙基三甲基氟化铵壳聚糖、羟丙基三甲基氯化铵壳聚糖和羟丙基三甲基溴化铵壳聚糖中的一种或者多种。
3.如权利要求1所述的一种可控有序介孔二氧化硅微球的制备方法，其特征在于：S2中所述无机硅源为碱性硅溶胶，其SiO2干基含量为20-50％；所述有机硅源为正硅酸四乙酯、正硅酸四甲酯、正硅酸四丙酯和正硅酸四丁酯中的一种或者多种。
4.如权利要求1所述的一种可控有序介孔二氧化硅微球的制备方法，其特征在于：S3中所述矿化剂为氨水、十二胺、尿素、二乙醇胺、三乙胺和二乙胺中的一种或多种。
5.如权利要求1所述的一种可控有序介孔二氧化硅微球的制备方法，其特征在于：S1中结构导向剂和去离子水的混合温度为40-80℃。
6.如权利要求1所述的一种可控有序介孔二氧化硅微球的制备方法，其特征在于：S4中所述焙烧温度为500-650℃。
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